US3285957A - Diphenyl semicarbazides - Google Patents
Diphenyl semicarbazides Download PDFInfo
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- US3285957A US3285957A US344539A US34453964A US3285957A US 3285957 A US3285957 A US 3285957A US 344539 A US344539 A US 344539A US 34453964 A US34453964 A US 34453964A US 3285957 A US3285957 A US 3285957A
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- US
- United States
- Prior art keywords
- dichlorophenyl
- semicarbazides
- grams
- mol
- semicarbazide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- FDPGUECLKNPLOB-UHFFFAOYSA-N (n-phenylanilino)urea Chemical class C=1C=CC=CC=1N(NC(=O)N)C1=CC=CC=C1 FDPGUECLKNPLOB-UHFFFAOYSA-N 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 7
- -1 DIPHENYL SEMICARBAZIDES Chemical class 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 150000003349 semicarbazides Chemical class 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Chemical group 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 4
- YMJSQPNVQRHZDW-UHFFFAOYSA-N (3,4-dichlorophenyl)hydrazine Chemical compound NNC1=CC=C(Cl)C(Cl)=C1 YMJSQPNVQRHZDW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- GLCIMEOOSALMQT-UHFFFAOYSA-N 1,2,3-trichloro-5-isocyanatobenzene Chemical compound ClC1=CC(N=C=O)=CC(Cl)=C1Cl GLCIMEOOSALMQT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- CEQXZSPTHJWSPZ-UHFFFAOYSA-N (3,4,5-tribromophenyl)hydrazine Chemical compound NNC1=CC(Br)=C(Br)C(Br)=C1 CEQXZSPTHJWSPZ-UHFFFAOYSA-N 0.000 description 1
- UNGXYLFIPXXYDT-UHFFFAOYSA-N (3,4,5-trichlorophenyl)hydrazine Chemical compound NNC1=CC(Cl)=C(Cl)C(Cl)=C1 UNGXYLFIPXXYDT-UHFFFAOYSA-N 0.000 description 1
- GAJWNTLEKRZSTO-UHFFFAOYSA-N (3,4-dibromophenyl)hydrazine Chemical compound NNC1=CC=C(Br)C(Br)=C1 GAJWNTLEKRZSTO-UHFFFAOYSA-N 0.000 description 1
- DSEXYRJTIPASEZ-UHFFFAOYSA-N 1,2-dibromo-4-isocyanatobenzene Chemical compound BrC1=CC=C(N=C=O)C=C1Br DSEXYRJTIPASEZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LSKOIJNKBNPPLK-UHFFFAOYSA-N 1-anilino-3-(3,4-dichlorophenyl)urea Chemical compound C1=C(Cl)C(Cl)=CC=C1NC(=O)NNC1=CC=CC=C1 LSKOIJNKBNPPLK-UHFFFAOYSA-N 0.000 description 1
- NGZZNUMYERKSQA-UHFFFAOYSA-N 1-anilino-3-phenylurea Chemical class C=1C=CC=CC=1NC(=O)NNC1=CC=CC=C1 NGZZNUMYERKSQA-UHFFFAOYSA-N 0.000 description 1
- CZQIJQFTRGDODI-UHFFFAOYSA-N 1-bromo-4-isocyanatobenzene Chemical compound BrC1=CC=C(N=C=O)C=C1 CZQIJQFTRGDODI-UHFFFAOYSA-N 0.000 description 1
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 description 1
- MFUVCHZWGSJKEQ-UHFFFAOYSA-N 3,4-dichlorphenylisocyanate Chemical compound ClC1=CC=C(N=C=O)C=C1Cl MFUVCHZWGSJKEQ-UHFFFAOYSA-N 0.000 description 1
- 241000499489 Castor canadensis Species 0.000 description 1
- 235000011779 Menyanthes trifoliata Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
Definitions
- This invention relates to a novel class of diphenyl semicarbazides. More particularly, this invention is concerned with a class of new organic compounds which are, 1,4-diphenyl semicarbazides wherein each of the phenyl groups contains at least one halogen substituent. Such semicarbazides are found to possess useful and unexpected biological activity.
- novel compounds of this invention have the general formula,
- each X is selected from the group consisting of chlorine and bromine
- each Y is selected from the group consisting of hydrogen, chlorine and bromine.
- the total number of halogen substituents is from three to six.
- the semicarbazides of this invention can be prepared by causing a halophenyl isocyanate to react with a substantially equimolar amount of a halophenyl hydrazine.
- the reactants are generally heated, although specific reaction temperatures will vary depending primarily upon the particular isocyanate and hydrazine employed.
- an inert organic solvent for the reactants.
- suitable solvents are benzene, toluene, xylene, hexane, heptane, octane, ethyl ether, tetrahydrofuran, dioxane, trichloroethylene and the like.
- Example I A suitable reaction vessel is charged with 1.9 grams (0.01 mol) of 3,4-dichlorophenyl isocyanate, 1.8 grams (0.01 mol) of 3,4-dichlorophenyl hydrazine and 200 ml. of ether. The reactants are mixed and heated to reflux temperature. The heating is continued for a period of about three hours, during which time solids are formed. The reaction mixture is then cooled, and the solids are collected by filtration. Said solids are recrystallized twice from toluene to yield 1,4-bis(3,4-dichlorophenyl) semicarbazide, M.P. 204'205 C.
- Example II Following the procedure set forth in Example I, the reactants employed are 2.2 grams (0.01 mol) of 3,4,5- trichlorophenyl isocyanate and 2.70 grams (0.01 mol) of 3,4-dibromophenyl hydrazine. The product obtained is identified as 1-(3,4-dibromophenyl)-4-(3,4,5-trichlorophenyl) semicarbazide.
- Example III Following the procedure set forth in Example I, the reactants employed are 3.9 grams (0.02 mol) of 4-bromophenyl isocyanate and 6.9 grams (0.02 mol) of 3,4,5-tribromophenyl hydrazine. The product obtained is identifled as 1-(3,4,5-tribromophenyl-4-(4-bromopheny1) semicarbazide.
- Example IV Following the procedure set forth in Example I, the reactants employed are 2.8 grams (0.01 mol) of 3,4-dibromophenyl isocyanate and 1.8 grams (0.01 mol) of 3,4-dichlorophenyl hydrazine. The product obtained is identified as 1 (3,4-dichlorophenyl) 4 (3,4-dibromophenyl) semicarbazide.
- Example V A suitable reaction vessel is charged with 3.5 grams (0.02) mol of 3,4-dichlorophenyl hydrazine, 3.1 grams (0.02 mol) of 4-chlorophenyl isocyanate and 250 ml. of ether. The reactants are mixed and heated to reflux temperature. The heating is continued for about one hour, during which period solids are formed. The reaction mixture is then cooled, and the solids are collected by filtration. Said solids are washed with ether and dried. Recrystallization from ohlorobenzene yields 1-(3,4-dichlorophenyl)-4-(4-chlorophenyl) semicarbazi-de, M.P. 215-2l6 C.
- Example VI Following the procedure set forth in Example V, the reactants employed are 2.2 grams (0.01 mol) of 3,4,5-trichlorophenyl isocyanate and 2.1 grams (0.01 mol) of 3,4,5-trichlorophenyl hydrazine. The product obtained is identified as 1,4-bis(3,4,5-triohlorophenyl) semicarbazide.
- the semicarbazides of this invention possess useful biological activity. They are particularly effective in controlling the growth of bacterial organisms.
- both 1,4-bis(3,4-dichlorophenyl) semicarbazide and l-(3,4-dichlorophenyl)-4-(4-chlorophenyl) semicarbazide were shown to be active against Staphylococcus aureus.
- the latter displayed effective control of the organ-ism at a dilution in excess of one part per one hundred thousand, and the former displayed such control at a dilution in excess of one part per one million. Similar activity is shown by other and different semicarbazides of this invention.
- Such related compounds include: (a) 1-phenyl-4-(3,4- dichlorophenyl) semicarbazide (J. Am. Chem. Soc., vol. 79, p. 1245); (b) 1-(3,4-dichlorophenyl-4-pheny1 semicarbazi-de; (c) 1-(3,4-dichlorophenyl)-4-phenyl thiosemicarbazide; (d) 1-(3,4-dichlorophenyl)-4-(3-chlorophenyl) semicarbazide; and (e) 1-(3,4-dichlorophenyl)-4-(2,4,6- trichlorophenyl) semicarbazide.
- Compounds (a), (b) and (e) were found to have a maximum effective delution of only one part per one thousand, while Compounds (0) and (d) were ineffective even at that relatively high concentration.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent 3,285,957 DIPHENYL SEMICARBAZIDES Joseph Willard Baker, Kirkwood, and Raymond Eugene Stenseth, Webster Groves, Mo, assignors to Monsanto Company, a corporation of Delaware No Drawing. Filed Feb. 13, 1964, Ser. No. 344,539 Claims. (Cl. 260554) This invention relates to a novel class of diphenyl semicarbazides. More particularly, this invention is concerned with a class of new organic compounds which are, 1,4-diphenyl semicarbazides wherein each of the phenyl groups contains at least one halogen substituent. Such semicarbazides are found to possess useful and unexpected biological activity.
The novel compounds of this invention have the general formula,
wherein each X is selected from the group consisting of chlorine and bromine, and each Y is selected from the group consisting of hydrogen, chlorine and bromine. As is apparent from said formula, the total number of halogen substituents is from three to six.
The semicarbazides of this invention can be prepared by causing a halophenyl isocyanate to react with a substantially equimolar amount of a halophenyl hydrazine. The reactants are generally heated, although specific reaction temperatures will vary depending primarily upon the particular isocyanate and hydrazine employed. In practicing such preparations, it is preferred to use an inert organic solvent for the reactants. Among the suitable solvents are benzene, toluene, xylene, hexane, heptane, octane, ethyl ether, tetrahydrofuran, dioxane, trichloroethylene and the like.
The invention will be more fully understood by reference to the following examples which are set forth herein solely for the purpose of illustration, and they are not to be construed as limiting the scope of the present invention.
Example I A suitable reaction vessel is charged with 1.9 grams (0.01 mol) of 3,4-dichlorophenyl isocyanate, 1.8 grams (0.01 mol) of 3,4-dichlorophenyl hydrazine and 200 ml. of ether. The reactants are mixed and heated to reflux temperature. The heating is continued for a period of about three hours, during which time solids are formed. The reaction mixture is then cooled, and the solids are collected by filtration. Said solids are recrystallized twice from toluene to yield 1,4-bis(3,4-dichlorophenyl) semicarbazide, M.P. 204'205 C.
Example II Following the procedure set forth in Example I, the reactants employed are 2.2 grams (0.01 mol) of 3,4,5- trichlorophenyl isocyanate and 2.70 grams (0.01 mol) of 3,4-dibromophenyl hydrazine. The product obtained is identified as 1-(3,4-dibromophenyl)-4-(3,4,5-trichlorophenyl) semicarbazide.
Example III Following the procedure set forth in Example I, the reactants employed are 3.9 grams (0.02 mol) of 4-bromophenyl isocyanate and 6.9 grams (0.02 mol) of 3,4,5-tribromophenyl hydrazine. The product obtained is identifled as 1-(3,4,5-tribromophenyl-4-(4-bromopheny1) semicarbazide.
Example IV Following the procedure set forth in Example I, the reactants employed are 2.8 grams (0.01 mol) of 3,4-dibromophenyl isocyanate and 1.8 grams (0.01 mol) of 3,4-dichlorophenyl hydrazine. The product obtained is identified as 1 (3,4-dichlorophenyl) 4 (3,4-dibromophenyl) semicarbazide.
Example V A suitable reaction vessel is charged with 3.5 grams (0.02) mol of 3,4-dichlorophenyl hydrazine, 3.1 grams (0.02 mol) of 4-chlorophenyl isocyanate and 250 ml. of ether. The reactants are mixed and heated to reflux temperature. The heating is continued for about one hour, during which period solids are formed. The reaction mixture is then cooled, and the solids are collected by filtration. Said solids are washed with ether and dried. Recrystallization from ohlorobenzene yields 1-(3,4-dichlorophenyl)-4-(4-chlorophenyl) semicarbazi-de, M.P. 215-2l6 C.
Example VI Following the procedure set forth in Example V, the reactants employed are 2.2 grams (0.01 mol) of 3,4,5-trichlorophenyl isocyanate and 2.1 grams (0.01 mol) of 3,4,5-trichlorophenyl hydrazine. The product obtained is identified as 1,4-bis(3,4,5-triohlorophenyl) semicarbazide.
As noted above, the semicarbazides of this invention possess useful biological activity. They are particularly effective in controlling the growth of bacterial organisms. In a representative test, both 1,4-bis(3,4-dichlorophenyl) semicarbazide and l-(3,4-dichlorophenyl)-4-(4-chlorophenyl) semicarbazide were shown to be active against Staphylococcus aureus. The latter displayed effective control of the organ-ism at a dilution in excess of one part per one hundred thousand, and the former displayed such control at a dilution in excess of one part per one million. Similar activity is shown by other and different semicarbazides of this invention.
The above-illustrated control of bacterial organisms is both unexpected and unpredictable. The presence of the halogen atoms at the 3 and 4 positions of the azino phenyl ring, and also the presence of a halogen atom at the 4 position of the carbamoyl phenyl ring, appear to be the significant factors. In order to demonstrate the distinctive nature of the limited group of semicarbazides of this invention, a number of closely relate-d compounds were prepared and tested against the same bacterial organism.
Such related compounds include: (a) 1-phenyl-4-(3,4- dichlorophenyl) semicarbazide (J. Am. Chem. Soc., vol. 79, p. 1245); (b) 1-(3,4-dichlorophenyl-4-pheny1 semicarbazi-de; (c) 1-(3,4-dichlorophenyl)-4-phenyl thiosemicarbazide; (d) 1-(3,4-dichlorophenyl)-4-(3-chlorophenyl) semicarbazide; and (e) 1-(3,4-dichlorophenyl)-4-(2,4,6- trichlorophenyl) semicarbazide. Compounds (a), (b) and (e) were found to have a maximum effective delution of only one part per one thousand, while Compounds (0) and (d) were ineffective even at that relatively high concentration.
While the invention has been described herein with regard to several specific embodiments, it not so limited. It is to be understood that modifications and variations of said invention, obvious to those skilled in the art, may be made without departing from the spirit and scope as hereinafter defined.
The embodiments of the invention in which an exclu- 3 4 sive property or privilege is claimed are defined as fol- 5. 1-(3,4-dibr0mophenyl)-4-(4-bromopheny1) semicarlows bazide.
1. A compound of the formula,
References Cited by the Examiner Y Y UNITED STATES PATENTS if 2,658,062 11/1953 Jones 260-554 X 2,855,435 10/1958 Grillot et a1 260544 2,959,615 11/1960 Lum et al 260544 X Y 3,021,258 2/1962 Haynes 167-30 10 3,113,070 12/1963 Pluijgers et a1 167-30 wherein each X is selected from the group consisting of chlorine and bromine, and each Y is selected from tne OTHER REFERENCES group consisting of hydrogen, chlorine and bromine. Beaver et 21].: J. Amer. Chem. Soc., vol. 79 (1957),
2. 1,4-bis(3,4-dich1orophenyl) semicarbazide. r pages 1236-45, 3. 1,4-bis(3,4-dibromopheny1) sernicarbazide.
4. 1-(3,4-dichlorophenyl)-4-(4-chl0rophenyl) semicar- ALEX MAZEL Pl'imm'y Examiner bazide. HENRY R. JILES, Assistant Examiner.
Claims (1)
1. A COMPOUND OF THE FORMULA,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US344539A US3285957A (en) | 1964-02-13 | 1964-02-13 | Diphenyl semicarbazides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US344539A US3285957A (en) | 1964-02-13 | 1964-02-13 | Diphenyl semicarbazides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3285957A true US3285957A (en) | 1966-11-15 |
Family
ID=23350948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US344539A Expired - Lifetime US3285957A (en) | 1964-02-13 | 1964-02-13 | Diphenyl semicarbazides |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3285957A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0144853A2 (en) * | 1983-11-21 | 1985-06-19 | Fujisawa Pharmaceutical Co., Ltd. | Semicarbazide derivatives, processes for preparation thereof and pharmaceutical composition comprising the same |
| EP0727708A1 (en) * | 1995-02-15 | 1996-08-21 | Fuji Photo Film Co., Ltd. | Color developing agent, silver halide photographic light-sensitive material and image forming method |
| US5756275A (en) * | 1995-11-30 | 1998-05-26 | Fuji Photo Film Co., Ltd. | Color-developing agent, silver halide photographic light-sensitive material and image-forming method |
| US5874203A (en) * | 1995-11-30 | 1999-02-23 | Fuji Photo Film, Co., Ltd. | Color-developing agent, silver halide photographic light-sensitive material and image-forming method |
| US5889163A (en) * | 1995-11-30 | 1999-03-30 | Fuji Photo Film Co., Ltd. | Method for producing azo dye compounds |
| US6103458A (en) * | 1996-08-02 | 2000-08-15 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic light-sensitive material |
| US20040034072A1 (en) * | 2000-08-21 | 2004-02-19 | Werner Mederski | Aza-amino acid derivatives (factor Xa inhibitors 15) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2658062A (en) * | 1949-09-17 | 1953-11-03 | Standard Oil Dev Co | Mineral oil additive |
| US2855435A (en) * | 1958-03-27 | 1958-10-07 | Grace W R & Co | Substituted hydrazines by reaction of dichlorourea with amines |
| US2959615A (en) * | 1957-10-09 | 1960-11-08 | Nat Distillers Chem Corp | Preparation of substituted semicarbazides |
| US3021258A (en) * | 1958-10-06 | 1962-02-13 | Union Carbide Corp | Diphenyl sulfide nematocide |
| US3113070A (en) * | 1961-01-05 | 1963-12-03 | Philips Corp | Method of combating fungi with thiobenzamide |
-
1964
- 1964-02-13 US US344539A patent/US3285957A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2658062A (en) * | 1949-09-17 | 1953-11-03 | Standard Oil Dev Co | Mineral oil additive |
| US2959615A (en) * | 1957-10-09 | 1960-11-08 | Nat Distillers Chem Corp | Preparation of substituted semicarbazides |
| US2855435A (en) * | 1958-03-27 | 1958-10-07 | Grace W R & Co | Substituted hydrazines by reaction of dichlorourea with amines |
| US3021258A (en) * | 1958-10-06 | 1962-02-13 | Union Carbide Corp | Diphenyl sulfide nematocide |
| US3113070A (en) * | 1961-01-05 | 1963-12-03 | Philips Corp | Method of combating fungi with thiobenzamide |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0144853A2 (en) * | 1983-11-21 | 1985-06-19 | Fujisawa Pharmaceutical Co., Ltd. | Semicarbazide derivatives, processes for preparation thereof and pharmaceutical composition comprising the same |
| EP0144853A3 (en) * | 1983-11-21 | 1986-01-29 | Fujisawa Pharmaceutical Co., Ltd. | Semicarbazide derivatives, processes for preparation thereof and pharmaceutical composition comprising the same |
| US4725608A (en) * | 1983-11-21 | 1988-02-16 | Fujisawa Pharmaceutical Co., Ltd. | Semicarbazide derivatives, processes for preparation thereof and pharmaceutical composition comprising the same |
| EP0727708A1 (en) * | 1995-02-15 | 1996-08-21 | Fuji Photo Film Co., Ltd. | Color developing agent, silver halide photographic light-sensitive material and image forming method |
| US5780210A (en) * | 1995-02-15 | 1998-07-14 | Fuji Photo Film Co., Ltd. | Color developing agent, silver halide photographic light-sensitive material and image forming method |
| US5756275A (en) * | 1995-11-30 | 1998-05-26 | Fuji Photo Film Co., Ltd. | Color-developing agent, silver halide photographic light-sensitive material and image-forming method |
| US5874203A (en) * | 1995-11-30 | 1999-02-23 | Fuji Photo Film, Co., Ltd. | Color-developing agent, silver halide photographic light-sensitive material and image-forming method |
| US5889163A (en) * | 1995-11-30 | 1999-03-30 | Fuji Photo Film Co., Ltd. | Method for producing azo dye compounds |
| US6103458A (en) * | 1996-08-02 | 2000-08-15 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic light-sensitive material |
| US20040034072A1 (en) * | 2000-08-21 | 2004-02-19 | Werner Mederski | Aza-amino acid derivatives (factor Xa inhibitors 15) |
| US6849626B2 (en) * | 2000-08-21 | 2005-02-01 | Merck Patent Gmbh | Aza-amino acid derivatives (factor Xa inhibitors 15) |
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